Process of treating crude oil of the pennsylvania type



Patented Jan. 1,3, 1931 UNITED vs'rlvi-las PATENT; OFFICE WALTER s BAYLIs, or' Los ANGELES, cALrroBNA, AssreNon, BY unsNE ASSIGN- MENTS, 'ro rrLTnoL COMPANY or CALIFORNIA, or Los ANGELEs, cALIronNrA, A

CQRPOBATION 0F CALIFORNIA c rnocnss or rnEA'rING emma 011. -or THE rENNsYLvAN-IA ma Application `ilecl November 12, 1927. Serial No. 282,739.

A My invention relates to the art of refining pfpetroleum. 'Petroleum comprises a mixture of a'large number of hydrocarbons, the boiltroleum products, each of which com rises a group of said hydrocarbons, the oiling pointsof which are grouped fairly close together. Included in such products and named in order of decreasin bollingpoints are the following: tar, para grease, lubricating oil, distillate, kerosene, and gasoline.

' In this fractional distillation there is usually a certain amount of decomposition of the hydrocarbons. into carbones, asphaltenes, and unsaturated hydrocarbonsl which discolor the product and which must Abe removed in order for the product to be marketable. It is common practice to accomplish this by treating the refined product successively with sulphuric acid and caustic soda. The acid and alkali treatment eiects the desired purpose but produces large quantities -of sludge or `soapy substance vwhich result from chemical union between the petroleum product being rened and the chemicals. Thus, being refined 'are wasted. v

It is an object of my invention to provide a process for removing impurities from a of sludge.

purifying process petroleum product `without the formation Moreover, the cost of the chemicals used in the acid and alkali process is considerable and it is correspondingly an object of my invention` to provide a process of purifying a petroleum product in whichy this expense 1s substantially eliminated. It has been previously known that cert 1n 'impurities can be removed from etroleum roducts after these products ad .been ormed fromcrude petroleum by fractlonal distillation by the use ofa suitable adsorptive agent such as acid-treated earth. The.

application of suclladsorptive agent in the product to 'bepuried had been condensed and cooled. The effe tiveness ofthe .adsorp-V considerable quantities of the product' ofthe agitator 12 been 'made after the tive agent when applied in this manneri is quite low.

Itis therefore a further object of m in-4 vention to provide a process of puri ing petroleum products with an adsorptive agent 1n which the effectiveness of the latter is materially increased.

While the process of my invention maybe used in treating many di'erent petroleum products, it is best adapted for use in ren-A ing lubricating oil from a crude petroleum whichdoes not contain tar and asphalt. Y The process of my invention is particularl adaptable to the treatment of erudefl oils suc as the -paraiiin base Pennsylvania oil which has no tar orA asphalt' content and will be described in connection4 with treating such a Leading from a suitable. source of supply of parain baseand crude oil and discharging into the agitator 12 is a crude oil supply pipe p end of. the agitator 12 is an 'adso tive-material-feed ,pipe 37. Disposed within the 36. Also discharging into the upper.'

agitator 12 is an -agitating rotor 38'wl1ich is I as by the gears 39. Connectin the lower end with the 1n-take; of .the pump 13 -is a pipe V40, discharge end of the pump 13 with the in-take end of the seriesof heat exchangers 14 is a pipe 41. Connected 'with the pipe 41 at an 1 elbow thereof is a steamv pipe-42 having a valve -43. Connecting the outlet end of thel series of heat exchangers 14 with the in-take end of the pipe still l5 is api 45. The pipe still 15 is heated in any suit-a le' manner as by ladapted to be rotatedin any suitable manner n v .while connecting the fuel supplied by a\burner 46. The discharge scribed in carrying out't-he process of my in'- end of the still 1 5 isconnected to an intermediate portion of the atmospheric column 16 by a pipe 48. Beneath the point at which the pipe 48 enters the co-lumn 16, a series of baiile plates 49 and 50 -is disposed in alternating relation so that any liquid discharge-d through the pipe 48 into the column 16 must pass in a circuitous route from the point of discharge to the bottom of the column 16.

Disposed in the atmospheric column' 16 above the point at which the pipe 48 connects thereto are pairs 55 of baie plates 49 and50. These pairs 55 are positioned in spaced relation so as to make room between adjacent pairs of co-llector pans 56. Each of the collector pans 56 is connected by a pipe 57 to one of the hea-t exchangers 14 from which pipes 58 lead to suitable distillate storage tanks". Leading from the-upper end of the atmospheric column -16 is a gasoline vapor line 60.

Connecting the lower en'd of the atmospheric column 16 to the inlet end of the cooler 17- is a pipe 61. Connecting the discharge end of the cooler 17 to the inlet end of the pump 18 is a pipe 62 into which a solvent pipe 63 connects. The discharge end of the pump 18 is connected to the filter press 19 by aV pipe 64. The filterv press 19 may be any suitable type ofpr'ess, but it is preferably a. Sweetland press. Leading from this press is a liquol discharge pipe 65. n

.The operationof the apparatus above devention is as follows: v

The process is designed to be'continuous and a continuous supply of crude oil is therefore fed through the pipe 36l in to the agitator 12. .At the Sametime a continuous supply of a suitable adsorptiveagent, which is preferably the acid-treated-clay known to the trade as FiltroPbut which may be any of the y.the temperature "of the mixture is `gradually` raised in its passage through the series ofother well known adsorptive clays, is lfed into the agitator 12v through the pipe 37. The agitator rotor 38 is rotated constantly so as to mix the crude oil and the adsorptive agent as4 these are fed intothe agitator 12. The.

mixture of'crude oil and adsorptive agent is drawn. from -the bottom of the agitator l2 through the pipe 40 by the pump 13 and dis# charged through the pipe 41 intothe upper end ofthe series of heat exchangers 14. At this point, the valve 43 may be openedand steam forced into the mixture so .as to raise,

the temperature of' the mixture and accelerate any adsorptive tendency which the ad#- sorptive agent mayhave on the crude oil as heat exchangers 14.

The mixture-usually enters'the first of the heat exchangers 14 at a temperature of ap-V proximately 240 F.- and leaves the last of the vheat exchangers 14 through which it passes at a temperature of. approximately410o F.' The mixture is then conducted through the flow" of mixture through this pipe 45 to the pipe still 15, where it is raised to a temperature of substantially. 750o F., at which temperature itis discharged from the pipe 48 into the atmospheric column 16. The mixture, entering the column 16, flows down through a circuitous path over the baffle plates 49 and 50 andreleases all of the lighter fractions of the crude oil so that the residuum which collects in the lower end of the column 16 comprises'a mixture of fractions which is termed cylinder stock and which has an average density of 26 B.

The various fractions of crude oil which pass upward through the column 16 in the form of vapors are condensed and cooled in the various pans 56, 'and flowing outward through the heat exchangers 14, effect a rise of thel temperature of.' the crude oil and adsorptive-agent mixture as previously menl tioned. .Any gasoline vapor which is not condensed in the upper of the pans 56 passes from the column 16 through the gasoline vapor line 6() to a suitable condenser, not shown. The various fractions thus condensed in 'the column 16, in order of decreasing boiling points, may include the following:

lThe cylinder stock which collects in the lower end of the column 16 flows through the cooler 17 and thepipe 62 to the pump 18.

At this time a suitable solvent is introduced through the pipe 63 into the cylinder stock so that it may be handledmore easily by the pump 18 and 'filter 19. The pump 18 forces the diluted cylinder stock through the pipe 6 3 into the filter press 19 which 'retains thev adsorptive'clay and permits the purified cylinder stock to be discharged through the. pipe 65 which conducts it lt0 a suitable place of storage. When a suiiicient amount of cake has been formed in the filter ipress 19, the

stoppedand .switched to another similar filter press held in readiness'for this purpose. The cake in the .lter press 19 is then washed 'with a vsuitable solvent so as -to remove any. of. the remaining cylinderv lter press is stock from the cake. Suitable provision may I also be made for blowing the cake in the press with air and steam after removing the re-- tained oil so as to drive out the excess of solvent'and dry 4the cake. Thereafter the filter press is opened and the cake removed and conveyed by any suitable means, such as a. belt conveyor, -to the reactivating house where the clay is reactivated so as to again be suitable for use in the 'above described process.

As statedv above, this-process has been partiuularly successful with the use of Filtrol,

state. Thus, due to the enormous surfaces in v the Filtrol on which the acid is carried in a thin film, there is very powerful action on the oil, even when an extremely small amount of acid has been added to thev Filtrol.

Another greated advantage of usingnthe acid in this manner is that it acts upon the oil without being given up 4 by the Filtrol so that neutralization of the nal oil product is unnecessary.

' In addition to the advantages of my process above noted, the submitting ofthe crude oil to the complete fractionatinfr process in the presence of fthe acidified adsorptive agent puriies the oil by removing asphaltenes and unsaturated hydrocarbons which form in the stills and l5 while the oil is'being refined.

It is also desired to point out that the impure substances are absorbed by the adsorptive clay before the vapors are discharged from the mixture of oil and clay in the column 16, so that fractions condensed in the pans 56 of the column 16` are already purified andfurther treatment of these lis therefore unnecessary.

I claim as my invention:

1. The method of rening crude oil for the production of lubricating stock therefrom :which comprises mixing decolorizing clay with the oil, passing the resultant mixture through a heating zone and heating the same to a temperature sufiicient to vaporize lighter fractions of the crude oil, introducing the mixture to a fractionating zone at a ,oint substantially above thebottom thereo whereby unvaporized portions of the mixture descend toward the bottom of saidfractionating zone and released vapors ascend toward the top thereof, condensing heavier fractions of the released vapors in the portion of said fractionating zone above the point of introduction ofthe mixture therto, separatelywithdrawing the condensed fractions from the fractionating zone, removing lighter fractions of the released vapors from the topof said fractionating zone and subjecting the same to condensation, withdrawingthe mixture `of unvaporized lubricating stock and clay from the bottom of said fractionating v through a heating zone and heating the same to a temperature sucient tovaporize lighter fractions of the crudeoil, introducing'the mixture to a fractionating zone at a point substantially .above the bottom thereof whereby unvaporized portions' of the m1xture descend toward the bottom of said fractionatin zone and released vapors ascend toward t e top thereof, condensing fractions of the released va ors heavier than gasoline in the portion o said fractionatin zone above the point of introduction of the' eated mixture thereto, separately withdrawing the l condensed fractions from the fractionating zone, removing gasoline vapors from the top of said fractionating zone .and'subjecting the same to condensation, withdrawing the mixture of unvaporized lubricating stock and clay from the bottom of said fractionating zone, and separating the clay from said 1ubric-atingl stock.

3. The method of refining hydrocarbon oil forthe production of lubricating stock theres'` from which comprises mixing decolorizing clay with the oil, passingl the resultant mixture through a heating zone and heating thesame sufficiently to vaporize' lighter fractions of the oil, introducing the mixture to a sepa-l rating zoneat a point substantially above the bottom thereof, -passing the mixture downwardly toward the bottom of said separating zone in relatively thin layers to assist the release of vapors therefrom, condensing released vapors in the portion of said separat- A ing zone above the point of introduction ofA the mixturethereto, separately withdrawing condensed vapors from the separting zone, removing the mixture of'unvaporized lubricating stock and clay from the lower portionL of said separating zone, and separating the clay from said lubricating stock.

In testimony whereof, I have hereunto set my hand at New York, New York, this 3rd day of November, 1927. l

WALTER S. BAYLIS.

zone, and separating the clay from said lul bricating stock v 2. The method of refining crude oil for the production of lubricating stock therefrom which comprises mixing decolorizing clay with the oil, passing the resultant mixture CIIRTIFICAT or CORRECTION;

'ratemue 1,788,654. a l Granted January I3, 1931, Io

WALTER s. BAYLIs..

lt is hereby Certified that error appears in the lprinted specification 0f the above numbered patent requiring-correction as' follows: Page 3,l after line 35,. insert the following paragrapmv A novel and veryv importantfeature of my invention is thus seen to bethe treatment with an adsorptive agent of .the oil being distilled in both its liquid and vapor phases. Another novel feature of importance is treating these liquid and vapor phases as -they are interchangingwith 'each other by alternate vaporization and condensation. The purification of the various products intowhich the oil is divided is thus accomplished concurrently with thedistillation andwith an efficiency and purity of'product hitherto unknown.;l

and that the said Letters Patent shouldbe read with .this correcto'therein that the same may conform to the record of the case in the Patent Office. Signed and sealedV this 24th day of February, A. D. 1931.

-. I Ml lJe (Seal.) Acting Commissioner. of Patents.- 

